EP0487102A1 - Système pour la récupération et utilisation de gaz CO2 - Google Patents

Système pour la récupération et utilisation de gaz CO2 Download PDF

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Publication number
EP0487102A1
EP0487102A1 EP91119959A EP91119959A EP0487102A1 EP 0487102 A1 EP0487102 A1 EP 0487102A1 EP 91119959 A EP91119959 A EP 91119959A EP 91119959 A EP91119959 A EP 91119959A EP 0487102 A1 EP0487102 A1 EP 0487102A1
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EP
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Prior art keywords
gas
calcium
sulfite
carbonate
absorbent
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EP91119959A
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German (de)
English (en)
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EP0487102B1 (fr
Inventor
Toshikatsu Mori
Hisao Yamashita
Hiroshi Miyadera
Osamu Kuroda
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Hitachi Ltd
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Hitachi Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This invention relates to a system which recovers and utilizes CO2 gas contained in flue gas such as combustion gas, thereby reducing the quantity of CO2 gas emitted into the atmosphere and hence contributing to the solution to the green house effect.
  • a process for the separation and concentration of CO2 gas in which CO2 gas is absorbed in an alkaline solution such as monoethanolamine or a potassium carbonate solution and the resulting solution is then heated to release CO2 gas.
  • monoethanolamine is prone to decomposition and substantial thermal energy is required to heat the CO2-absorbing solution.
  • the above process is therefore accompanied by potential problems such that energy consumption may be increased, offensive odor may be generated by the product of decomposition and deleterious effects may arise with the processing state, i.e., the CO2 gas reduction.
  • the above absorbents are both strongly corrosive.
  • the combustion gas also contains acid gas such as sulfurous acid gas
  • the acid gas firmly bonds to the absorbent so that CO2 gas cannot be separated and recovered easily.
  • the absorbent therefore loses its effectiveness rapidly. Accordingly, the above conventional process cannot be applied in this case.
  • a first object of this invention is to provide a method and system effective for reducing the quantity of CO2 gas emitted from a fossil fuel burning facility, such as a thermal power plant, by separating and concentrating CO2 gas discharged from the fossil fuel burning facility, reducing the CO2 gas to methane, methanol or the like and recycling it as fuel.
  • a fossil fuel burning facility such as a thermal power plant
  • a second object of this invention is to provide a method and system in which CO2 gas is separated and recovered efficiently, especially from flue gas containing sulfurous acid gas in addition to CO2 gas, and is recycled effectively as fuel.
  • a method for the treatment of flue gas containing CO2 gas and SOx gas which comprises bringing the flue gas into contact with an absorbent which contains an alkaline earth metal compound, in order to recover the CO2 gas and SOx gas as the carbonate and sulfite respectively of the alkali earth metal.
  • flue gas examples include the combustion gases of fossil fuel emitted from thermal power plants and the like.
  • Fossil fuel and the like contain carbon and sulfur as components so that their combustion gases contain CO2 gas and SOx gases such as sulfurous acid gas.
  • the reaction system Upon recovery of the carbonate and the sulfite, it is preferable to control the feed quantity of the absorbent so that the reaction system can be maintained at a pH where at least one of the compounds, either the carbonate or the sulfite, is present in a solid form.
  • the carbonate of the alkaline earth metal is separated from the sulfite and then decomposed into CO2 gas and the alkaline earth metal compound, thereby making it possible to recover CO2 gas and also to regenerate the alkaline earth metal compound into the absorbent.
  • a method for the regeneration of CO2 gas which comprises reducing CO2 gas, which has been obtained according to the above aspect, with hydrogen to form a CO2 reduction product such as a hydrocarbon, e.g. methane, or an oxygen-containing hydrocarbon, e.g. methanol.
  • a CO2 reduction product such as a hydrocarbon, e.g. methane, or an oxygen-containing hydrocarbon, e.g. methanol.
  • the CO2 reduction product so obtained can be reused as fuel.
  • a recycling process for the regeneration of CO2 gas which comprises the following steps: (1) an absorption step in which CO2 gas in the combustion gas of fossil fuel is absorbed in a solution containing an alkaline earth metal compound; (2) a step in which CO2 gas is recovered to regenerate the absorbent by decomposing the carbonate and/or bicarbonate of the absorbent formed in the absorption step; (3) a reduction step in which CO2 gas thus recovered is reduced with hydrogen into a hydrocarbon or oxygen-containing hydrocarbon such as methane or methanol; and (4) a recirculation step in which the product of the reduction step is returned to a fossil fuel combustion furnace.
  • a recycling system for the regeneration of CO2 gas as a system to attain the objects described above.
  • the recycling system comprises a means for bringing flue gas, which contains CO2 gas and SOx gas, into contact with an absorbent containing an alkaline earth metal compound, thereby recovering CO2 gas and SOx gas, as the carbonate and sulfite, respectiely, of the alkaline earth metal; a means for feeding the absorbent to the recovery means; a means for decomposing the carbonate of the alkaline earth metal, out of the carbonate of the alkaline earth metal and the sulfite of the alkaline earth metal, into CO2 gas and the alkaline earth metal compound; and a means for reducing the resulting CO2 gas with hydrogen, thereby producing a CO2 reduction product for regeneration.
  • the quantity of CO2 gas to be discharged can be reduced using unlimited and clean solar energy while still operating existing thermal power systems.
  • the present invention therefore, can become a basic countermeasure against the green house effect.
  • the means for recovering CO2 gas and SOx gas is provided with at least one absorbing tower.
  • This means may be constructed such that both CO2 gas and SOx gas can be recovered in a common absorbing tower.
  • This means can be equipped with two or more absorbing towers.
  • a means for separating the carbonate of the alkaline earth metal and the sulfite of the alkaline earth metal from each other be installed.
  • the absorbing tower itself may of course be constructed to achieve this separation too.
  • the absorbent-feeding means can reuse, as an absorbent, an alkaline earth metal compound obtained by decomposition.
  • the absorbent-feeding means may be equipped with a device for measuring the pH at a discharge port of the carbonate and the sulfite of the alkaline earth metal in the absorbing tower and with a feed controller for controlling the feed quantity of the absorbent.
  • the absorbent-feeding means controls the feed quantity of the absorbent to maintain a pH at which at least one of the compounds, either the carbonate or the sulfite, is present in a solid form.
  • the carbonate may be either the carbonate or the bicarbonate.
  • an alkaline earth metal compound can be used, with a calcium compound being especially preferred.
  • a calcium compound it is preferable to select at least one compound from the group consisting of calcium carbonate, calcium oxide and calcium hydroxide. Minerals composed principally of at least one of the above compounds, such as limestone, can also be used. Incidentally, these compounds are used in a slurry form. The slurry concentration may be, for example, 2-30%, preferably 5-15%.
  • an absorbent in a quantity substantially equal to the stoichiometric quantity required for the conversion of sulfurous acid gas and CO2 gas, which have been absorbed and removed from the flue gas, to calcium sulfite and calcium bicarbonate, respectively.
  • a slurry composed of calcium sulfite particles and a calcium bicarbonate solution can be obtained after the absorption step, whereby the separation of the bicarbonate from the sulfite or vice versa is very easy.
  • the heat of the combustion gas and waste heat available inherently from the fossil fuel burning facility can be utilized.
  • Heat energy of about 100°C is necessary for the bicarbonate decomposition step, heat energy of about 900°C for the carbonate decomposition and heat energy of about 200-500°C for the CO2 gas reduction step.
  • Use of various waste heat as the above heat energy can enhance the effects of the present invention.
  • the absorbent When calcium hydroxide is employed as an absorbent, it is preferable to feed the absorbent in a quantity substantially equal to the stoichiometric quantity required for the conversion of sulfurous acid gas and CO2 gas, both absorbed and removed from flue gas, to calcium sulfite and calcium carbonate, respectively.
  • Use of calcium hydroxide in the method of the present invention can bring about a particularly high CO2 absorbing capacity because, in addition to its high capacity to absorb CO2 gas and sulfurous acid gas, the absorbing solution still has a CO2-absorbing capacity when it is taken out from the absorption step.
  • the feed quantity of the absorbent is controlled so that the pH of the absorbing solution at the end of the absorption step is maintained, at about 10.5 or higher, preferably about 12.
  • Calcium sulfite and calcium carbonate are separated from their slurry obtained in the absorption step. Then calcium sulfite is oxidized into gypsum, while calcium carbonate is decomposed into calcium oxide and CO2 gas. The resulting calcium oxide is hydrated into calcium hydroxide, which can be utilized again as an absorbent.
  • a mixed slurry of calcium sulfite and calcium carbonate is oxidized into a slurry of gypsum and calcium carbonate. Then, gypsum and calcium carbonate are separated. The resulting calcium carbonate is decomposed into calcium oxide and CO2 gas, whereas calcium oxide is converted by hydration into calcium hydroxide, which can be used again as an absorbent.
  • two absorbing towers may be employed, one for the absorption of sulfurous acid gas only and the other for the absorption of CO2 gas only, whereby calcium sulfite is obtained from the former tower and calcium bicarbonate from the latter tower.
  • the subsequent step of mutual separation of the sulfite and the bicarbonate can be omitted.
  • a single absorbing tower which has the functions of two towers, for example, by subjecting flue gas and an absorbing solution to countercurrent contact, obtaining calcium sulfite and calcium bicarbonate from a vertically-intermediate part of the absorbing tower and drawing calcium sulfite and calcium bisulfite from a bottom part of the tower.
  • a catalyst composed of at least one of alumina, silica and titania as a carrier component, at least one of nickel, iron, copper, chromium, zinc, ruthenium and palladium as an active component and at least one of lanthanum, cerium and yttrium as a cocatalyst component.
  • the catalyst may be free of any carrier.
  • a metal complex such as ethylenediaminetetraacetic acid, citric acid or nitrilotriacetic acid can be added.
  • the present invention permits the construction of a system wherein a boiler is provided to burn fossil fuel, the resulting flue gas is passed to the absorbing tower and the boiler uses as a part of its fuel a hydrocarbon or oxygen-containing hydrocarbon produced by the regeneration means described above.
  • this system can be incorporated into a thermal power plant system.
  • a water electrolyzer is usable as a means for producing the hydrogen to be used in the reduction of CO2 gas.
  • a solar cell can preferably be employed.
  • the recycling system for the regeneration of CO2 gas according to the present invention can be operated using electric power from a solar cell during daytime and any surplus power from the thermal power plant at night.
  • the discharge quantity of CO2 gas is expected to be 455 t/h.
  • the light-receiving area of a solar cell which is used to produce electric power for obtaining hydrogen by electrolysis, which will in turn be used for the reduction of CO2 gas may be about 5 million square meters at 10% energy conversion efficiency.
  • Such a treatment will result in the production of 4.3 x 103 kcal( 5 x 105 kW) in the form of regenerated fuel.
  • an aqueous solution of an alkaline metal salt such as potassium carbonate or sodium carbonate as an absorbent for CO2 gas have been known.
  • the above absorbent is good for acid gases such as CO2 gas and sulfurous acid gas, but a sulfite formed by the absorption of sulfurous acid gas and the sulfate formed by the oxidation of the sulfite does not have a CO2-absorbing capacity and in addition, they are dissolved in water along with the bicarbonate formed by the absorption of the CO2 gas. The sulfite and sulfate, therefore, cannot easily be separated from the bicarbonate.
  • One of features of the present invention resides in ingeniously utilizing characteristic properties of the carbonate, sulfite and sulfate of an alkaline earth metal to permit easy separation of the carbonate and/or the bicarbonate from the sulfite and/or the sulfate and also the regeneration of the absorbent from the carbonate and/or bicarbonate (production of concentrated CO2 gas) or in the fact that conditions enabling the above-mentioned separation and regeneration have been selected for the absorption and regeneration of CO2 gas by a calcium compound.
  • a calcium salt formed by sulfurous acid gas and another calcium salt formed by CO2 gas can be separated from each other when sulfurous acid gas and CO2 gas are absorbed simultaneously by using a slurry of an alkaline earth metal compound, particularly, a calcium compound such as calcium hydroxide or calcium carbonate.
  • the calcium salt formed by CO2 gas can be decomposed to recover CO2 gas at a high concentration and can also be regenerated as an absorbent.
  • the absorption step of the present invention has been designed in view of the properties of such an alkaline earth metal compound, particularly a calcium compound such as calcium hydroxide or calcium carbonate, for CO2 gas and sulfurous acid gas.
  • an alkaline earth metal compound particularly a calcium compound such as calcium hydroxide or calcium carbonate, for CO2 gas and sulfurous acid gas.
  • FIG. 1 is the block diagram showing the arrangement of the equipments in the CO2 gas recycling system as one embodiment of the present invention.
  • This embodiment is equipped with a boiler 2 for burning fossil fuel 1, which is a fuel containing at least carbon as a component, such as coal or oil; a fuel gas treatment sub-system for subjecting the combustion gas from the boiler 2 to NOx reduction and also to desulfurization and decarbonization; and a reduction treatment sub-system in which CO2 separated as a result of the carbonization is reduced.
  • fossil fuel 1 is a fuel containing at least carbon as a component, such as coal or oil
  • a fuel gas treatment sub-system for subjecting the combustion gas from the boiler 2 to NOx reduction and also to desulfurization and decarbonization
  • a reduction treatment sub-system in which CO2 separated as a result of the carbonization is reduced.
  • the flue gas treatment sub-system is equipped with an NOx reduction unit 3, which conducts NOx removal; an absorbing tower 10, which functions as a means for absorbing SOx, particularly SO2, and also CO2 gas; a thickener 12, which functions as a means for separating a solid component (calcium sulfite) and a liquid component (calcium bicarbonate) from each other, said components having been obtained in the absorbing tower 10; an oxidizing tank 13 which oxidizes calcium sulfite to form gypsum; a dewatering tank 14 which dewaters the resulting gypsum; and a decomposition tank 15 which functions as a means for decomposing calcium bicarbonate to obtain CO2 gas.
  • NOx reduction unit 3 which conducts NOx removal
  • an absorbing tower 10 which functions as a means for absorbing SOx, particularly SO2, and also CO2 gas
  • a thickener 12 which functions as a means for separating a solid component (calcium sulfite) and a liquid component (
  • the flue gas treatment sub-system has, as absorbent-feeding means, a pH measuring device 21 which measures the pH of the absorbing solution discharged from the absorbing tower 10 and a feed controller 22 which controls the feeding of calcium carbonate to the absorbing tower 10 according to the pH of the absorbing solution measured by the pH measuring device 21.
  • the feed controller 22 although not illustrated in FIG.1, is equipped with a mixer which mixes a replenishing calcium carbonate slurry with a recycled calcium carbonate slurry from the reduction treatment sub-system which will be described below; a pump for supplying the mixed slurry to the absorbing tower 10; and a control unit which controls the mixer and the pump.
  • the absorbing tower 10 may be provided, if necessary, with a recirculating means (unillustrated), such as a pump, for the recirculation of the internal absorbing solution.
  • a recirculating means such as a pump
  • Another pump or the like may also be provided, as needed, to discharge the absorbing solution to the outside.
  • the reduction sub-system comprises a reducing tower 4 in which CO2 gas obtained in the decomposition tank 15 is subjected to reduction with hydrogen to produce a fuel such as methane; a water electrolyzer 5, which produces hydrogen to be used in the above reduction; and a solar cell 6, which functions as an electric source for supplying d.c. power to the water electrolyzer 5.
  • a catalyst that is, a catalyst composed of alumina as a carrier component, nickel as an active component and lanthanum as a cocatalyst component.
  • calcium carbonate obtained upon separation of CO2 gas in the flue gas treatment sub-system is fed to the absorbing tower 10 for reuse.
  • methane or the like obtained in the reduction sub-system is fed to the boiler 2 for reuse.
  • Combustion gas which has been formed by burning fossil fuel 1 in the boiler 2, is subjected to NOx removal in the NOx reduction unit 3 as needed, and the resulting flue gas containing sulfurous acid gas and CO2 gas is introduced into the absorbing tower 10.
  • the flue gas is brought into contact with a calcium carbonate slurry, which serves as an absorbent, to allow the absorbent to absorb both the sulfurous acid gas and the CO2 gas.
  • the flue gas from which both the gases have been removed is then discharged from the absorbing tower 10.
  • an absorbing solution (slurry) containing calcium sulfite and calcium bicarbonate is obtained by controlling the feed quantity of the absorbent.
  • the feed quantity is controlled to bring the flue gas into contact with the absorbent in a quantity substantially equal to the stoichiometric quantity required for the conversion of sulfurous acid gas and CO2 gas, which are to be absorbed and removed from the flue gas, to calcium sulfite and calcium bicarbonate, respectively.
  • the pH of the absorbing solution is measured by the pH measuring device 21 and, based on the measuring result, the feed quantity of the absorbent is controlled by the feed control unit 22 so that the pH of the absorbing solution is maintained at about 8.
  • the absorbing solution is separated in the thickener 12 into solid calcium sulfite and a calcium bicarbonate solution.
  • the calcium sulfite is oxidized with air or the like into gypsum, which is then discharged from the system after having been dewatered in the dewatering tank 14.
  • the resulting calcium bicarbonate solution is introduced into the decomposition tank 15, where it is decomposed into CO2 gas and calcium carbonate.
  • the decomposition of the solution is conducted under heat and the resulting calcium carbonate is returned as an absorbent to the absorbing tower 10 together with fresh calcium carbonate which is fed additionally.
  • the thermal decomposition requires a temperature of about 100°C.
  • the flue gas can be used as the heat source for this process.
  • the decomposition of calcium bicarbonate can be conducted by changing a gypsum-forming mother liquor as needed.
  • gypsum is produced together with CO2 gas.
  • Gypsum is fed to the absorbing tower together with calcium carbonate, and then discharged from the system with the gypsum produced above by the oxidation of calcium sulfite.
  • Highly-concentrated CO2 gas formed in the decomposition tank 15 is introduced into the reducing tower 4, and is converted to methane, methanol or the like with hydrogen obtained by hydrolysis in the water electrolyzer 5 using, for example, electric power from the solar cell 6.
  • the reduction product is used as fuel for the boiler.
  • FIG. 2 is a block diagram of a CO2 gas recycling system according to another embodiment of the present invention.
  • the flue gas treatment sub-system of this embodiment comprises, in addition to the units of the embodiment of Example 1, a dewatering device 16 which removes water from calcium carbonate formed in the decomposition tank 15; another decomposition tank 17, in which the dewatered calcium carbonate is heated and decomposed to obtain CO2 gas and calcium oxide; and a hydrating tank 18 in which the calcium oxide formed in the decomposition tank 17 is hydrolyzed with water obtained in the dewatering device 16 to produce calcium hydroxide.
  • the dewatering device 16, decomposition tank 17 and hydrating tank 18 are all installed after the decomposition tank 15. Incidentally, the CO2 gas obtained in the decomposition tanks 15 and 17 is introduced into the reducing tower 4.
  • flue gas containing sulfurous acid gas and CO2 gas is, in the absorbing tower 10, brought into contact with a calcium hydroxide slurry, which serves as an absorbent, to remove sulfurous acid gas and CO2 gas.
  • a calcium hydroxide slurry which serves as an absorbent, to remove sulfurous acid gas and CO2 gas.
  • an absorbing solution (slurry) containing calcium sulfite and calcium bicarbonate is obtained from the absorbing tower 10 by controlling the feed quantity of the absorbent. Namely, the feed quantity of the absorbent is controlled so that the flue gas can be brought into the absorbent in a quantity substantially equal to the stoichiometric quantity required to convert sulfurous acid gas and CO2 gas, which are to be absorbed and removed from the flue gas, to calcium sulfite and calcium bicarbonate, respectively.
  • the pH of the absorbing solution is measured by the pH measuring device 21, and the feed quantity of the absorbent is controlled by the feed control unit 22 so that the pH of the absorbing solution is maintained at about 8.
  • the absorbing solution is likewise separated, in the thickener 12, into solid calcium sulfite and a calcium bicarbonate solution.
  • Calcium sulfite is oxidized into gypsum with air or the like in the oxidizing tank 13.
  • the gypsum is then discharged from the system after having been dewatered in the dewatering tank 14.
  • the resulting calcium bicarbonate solution is, on the other hand, introduced into the decomposition tank 15, in which it is thermally decomposed into CO2 gas and calcium carbonate or, if a gypsum-forming mother liquor is added as needed, into CO2 gas and gypsum.
  • Example 2 The above procedures are conducted in a similar manner to Example 1, except that slaked lime is used as an absorbent.
  • calcium carbonate produced in the decomposition step is dewatered by the dewatering device 16, followed by the thermal decomposition into CO2 gas and calcium oxide in the decomposition tank 17.
  • the resulting calcium oxide is hydrated, in the hydrating tank 18, with water obtained by the dewatering device 16 to yield calcium hydroxide, which is then returned to the absorbing tower together with calcium hydroxide thus replenishing the system.
  • the resulting CO2 gas produced as a result of the decomposition of calcium bicarbonate is introduced into the reducing tower 4 together with hydrogen and, in a similar manner to Example 1, they are both reduced and recycled.
  • the decomposition of calcium carbonate requires a high temperature of about 900°C.
  • Calcium hydroxide is, however, superior to calcium carbonate in being able to absorb CO2 gas and sulfurous acid gas, thereby bringing about such advantages that the absorbing tower 10 can be reduced in size, and the recirculation velocity of the absorbing solution inside the absorbing tower can be lowered. In other words, the electric power for the recirculation pump can be reduced.
  • FIG. 3 is a block diagram of a CO2 gas recycling system according to a further embodiment of the present invention.
  • This embodiment is different from the embodiment of Example 2 in that calcium sulfite and calcium carbonate are obtained in the absorbing tower 10.
  • the decomposition tank 15 of Example 2 is omitted so that calcium carbonate discharged from the absorbing tower 10 is fed to the dewatering device 16, while CO2 gas is decomposed in the decomposition tank.
  • flue gas containing sulfurous acid gas and CO2 gas is brought into contact with a calcium hydroxide slurry, which is used as the absorbent, in the absorbing tower 10, whereby sulfurous acid gas and CO2 gas are eliminated.
  • the feed quantity of the absorbent is controlled to obtain from the absorbing tower 10 an absorbing solution (slurry) containing calcium sulfite and calcium carbonate.
  • the quantity of the absorbent is controlled so that the flue gas is brought into contact with the absorbent in a quantity substantially equal to the stoichiometric quantity required to convert sulfurous acid gas and CO2 gas, which are absorbed and removed from the flue gas, to calcium sulfite and calcium carbonate respectively.
  • the pH of the absorbent is measured by the pH measuring device 21, and the feed quantity of the absorbent is controlled by the feed control unit 22 so that the pH of the absorbent is maintained at around at least 10.5, preferably about 12.
  • the absorbing solution is separated into calcium sulfite and calcium carbonate in the decomposition tank 12.
  • the resulting calcium sulfite is, in the oxidizing tank 13, oxidized by air or the like into gypsum, which is dewatered in the dewatering tank 14 and then discharged from the system.
  • calcium carbonate is thermally decomposed into CO2 gas and calcium oxide in the decomposition tank 17, after having been dewatered in the dewatering device 16.
  • a gypsum-forming mother liquor may be charged as needed so that calcium carbonate is decomposed into CO2 gas and gypsum.
  • Calcium oxide is hydrated, in the hydration tank 18 with water obtained from the dewatering device 16, thereby forming calcium hydroxide.
  • the resulting calcium hydroxide is fed to the absorbing tower 10, together with calcium hydroxide thus replenishing the system.
  • the resulting CO2 gas is introduced into the reducing tower 4 and, in a similar manner to Example 1, reduced and then recycled.
  • the decomposition of calcium carbonate requires a high temperature of about 900°C.
  • a particularly high CO2-absorbing capacity is obtained, because calcium hydroxide has an excellent CO2 gas absorving capacity and sulfurous acid gas and, moreover, the absorbing solution can be drawn out from the absorbing tower in a state still retaining a CO2-absorbing capacity.
  • this embodiment has the advantages that the absorbing tower can be reduced in size and the recirculation velocity of the absorbing solution inside the absorbing tower can be lowered, in other words, the electric power for the recirculation pump can be reduced.
  • FIG. 4 is a block diagram of a CO2 gas recycling system according to a still further embodiment of the present invention.
  • This example is a variation of Example 3.
  • the system of this embodiment is similar to that of the embodiment shown in FIG.3 until an absorbing solution (slurry) containing calcium sulfite and calcium carbonate is obtained from the absorbing tower 10.
  • this embodiment is different from that of Example 3 in that the oxidizing tank 13 is arranged before the thickener 12 in order to oxidize the absorbing solution, which contains calcium sulfite and calcium carbonate, into gypsum and calcium carbonate. This is followed by the separation of the resulting gypsum and calcium carbonate from each other and then, by the decomposition of calcium carbonate.
  • Calcium oxide is hydrated, in the hydration tank 18, with water obtained by the dewatering device 16 in order to form calcium hydroxide, which is then fed to the absorbing tower 10 together with calcium hydroxide, thus replenishing the system.
  • the resulting CO2 gas is introduced into the reducing tower 4 where its reduction and recycling are conducted as in Example 1.
  • calcium carbonate and gypsum are separated from each other in the thickener 12.
  • the separation of calcium sulfite and calcium carbonate by this embodiment is easier than that by the embodiment of Example 3, because there is a large difference in particle size between calcium carbonate and gypsum (gypsum has a much larger particle size).
  • FIG. 5 is a block diagram of a CO2 gas recycling system according to a still further embodiment of the present invention.
  • This embodiment has obviated the mutual separation step of the sulfite and the carbonate, which is required in each of the embodiments previously described, by employing two absorbing towers.
  • One tower is used for the absorption of sulfurous acid gas only and the other for the absorption of CO2 gas only.
  • the system of this embodiment has one absorbing tower 10 for desulfurization and another absorbing tower 11 for decarbonization in the flue gas treatment sub-system thereof. After the absorbing tower 10, the oxidizing tank 13 and the dewatering tank 14 are arranged. After the absorbing tower 11, the decomposition tank 15 is disposed.
  • the thickener 12, which is included in each of the above embodiments is omitted. Further, these absorbing towers 10 and 11 are each equipped with the pH measuring device 21 and the feed control unit 22.
  • the remaining construction of this embodiment is similar to that of the embodiment of Example 1.
  • the flue gas is, in the absorbing tower 10, brought into contact with a calcium carbonate or calcium hydroxide slurry to form calcium sulfite.
  • the flue gas is then brought into contact with a calcium carbonate slurry in the absorbing tower 11, whereby a calcium bicarbonate solution is obtained.
  • the calcium sulfite from the absorbing tower 11 is discharged from the system following the oxidation in the oxidizing tank 13 and the dewatering in the dewatering tank 14.
  • the calcium bicarbonate is decomposed into calcium carbonate and CO2 gas in the decomposition tank 15.
  • the former is recycled into the absorbing tower 11, while the latter is fed to the reducing tower 4.
  • FIG. 6 is a block diagram of a CO2 gas recycling system according to a still further embodiment of the present invention.
  • This example is a variation of Example 5.
  • This embodiment has obviated the step for the mutual separation of the sulfite and the carbonate by employing two absorbing towers, one for the absorption of sulfurous acid gas alone, to form calcium sulfite and the other for the absorption of CO2 gas alone, to form calcium carbonate.
  • the decomposition tank 15, which is installed in Example 5 has been replaced by the dewatering device 16, the decomposition tank 17 and the hydration tank 18, as in Example 3.
  • the flue gas is first brought into contact with a calcium carbonate or calcium hydroxide slurry in the absorbing tower 10 in order to form calcium sulfite.
  • the flue gas is then brought into contact with a calcium hydroxide slurry in the absorbing tower 11 in order to form a calcium carbonate solution.
  • the calcium sulfite from the absorbing tower 11 is discharged from the system following the oxidation in the oxidizing tank 13 and the dewatering in the dewatering tank 14.
  • FIG. 7 is a block diagram of a CO2 gas recycling system according to a still further embodiment of the present invention.
  • a single absorbing tower is designed to perform both the functions of the two absorbing towers in Example 5 or 6.
  • the flue gas treatment sub-system in this embodiment is equipped with an absorbing tower 10 constructed such that a slurry can be drawn out from both an intermediate part and a bottom part.
  • the thickener 12 is constructed so as to receive the slurry from the intermediate part of the absorbing tower 10, while the oxidizing tank 13 is constructed so that calcium sulfite and calcium bisulfite, from the bottom part of the absorbing tower 10, as well as the thickener 12, can be oxidized there.
  • a calcium carbonate slurry is fed from a top part of the absorbing tower 10 and the flue gas is introduced from a lower part thereof, whereby the absorbent and the flue gas are subjected to countercurrent contact.
  • the slurry containing calcium sulfite and calcium bicarbonate and having pH 8 or so is discharged and introduced into the thickener 12.
  • the thickener 12 calcium sulfite and calcium bicarbonate are separated from each other.
  • the resulting calcium sulfite, together with calcium sulfite and calcium bisulfite discharged from the bottom part is oxidized into gypsum in the oxidizing tank 13.
  • the calcium bicarbonate is decomposed into calcium carbonate and CO2 gas in the decomposition tank 15.
  • the decomposition of calcium bicarbonate can also be conducted by optionally adding a gypsum-forming mother liquor.
  • gypsum is formed together with CO2 gas.
  • the resulting gypsum is, together with calcium carbonate, fed to the absorbing tower 10 and then, along with the above gypsum formed above by the oxidation of calcium sulfite, is discharged from the system.
  • Calcium carbonate formed in the decomposition tank 15 is, together with calcium carbonate replenished to the system, recycled to the absorbing tower 10, while the CO2 gas is fed to the reducing tower 4.
  • the boiler 2 was charged with 29.0 kg/h of coal as fossil fuel 1, and at the same time, a recycled gas containing 12.7 vol% of methane, 47.0 vol% of hydrogen and 10.6 vol% of CO2 gas from the reducing tower 4 was also charged. They were burned, whereby 311 Nm3/h of flue gas containing 12.89 vol% of CO2 gas and 0.24 vol% of sulfurous acid gas were produced. The resulting flue gas was introduced into the bottom part of the absorbing tower 10 through the NOx reduction unit 3.
  • ten perforated plates each having an opening rate of 40% were installed at varied stages.
  • 20.0 kg/h of a recycled slurry from the decomposition tank 15 said slurry containing 6.4 wt.% of calcium carbonate, and a replenishing slurry containing 10.0 wt.% of calcium carbonate were fed as a mixture and were then brought into contact with the flue gas in a countercurrent fashion.
  • the pH measuring device 21 was installed to measure the pH of the slurry mixture.
  • a solution containing 9.9 wt.% of calcium bicarbonate was discharged from an upper part of the thickener 12 at the rate of 328 kg/h and was then introduced into the decomposition tank 15.
  • a slurry containing 64.8 wt.% of calcium sulfite was, on the other hand, drawn out from a bottom part of the thickener 12 at the rate of 0.50 kg/h and was then introduced into the oxidation tank 13, in which air was blown into the slurry to oxidize the latter into calcium sulfate (gypsum).
  • Gypsum was next discharged from the bottom part of the dewatering tank 14 at the rate of 0.51 kg/h and was then separated.
  • the resulting CO2 gas was introduced into the reducing tower 4 together with 17.9 Nm3/h of hydrogen which had been produced in the water electrolyzer 5 using electricity generated from the 100 kW solar cell 6. It was brought into contact with 3 kg of a catalyst composed of nickel, lanthanum and alumina to convert the CO2 gas to methane, whereby 18.3 Nm3/h of gas containing 12.7 vol% of methane, 47.0 vol% of hydrogen and 10.6 vol% of CO2 gas was obtained.
  • the resulting gas was recirculated to the boiler 2 and was then burned together with coal.
  • the output of a generator (not shown) was 100 kW and 316 Nm3/h of flue gas containing 35.6 Nm3/h of CO2 gas were emitted from the stack.
  • the solar cell was employed as an energy source for the reduction sub-system in each of the above embodiments.
  • This invention is however not limited to the use of such a solar cell.
  • the electric power may be obtained from such a solar cell during the daytime and from any surplus power from the thermal power plant at night.

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  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Carbon And Carbon Compounds (AREA)
EP91119959A 1990-11-22 1991-11-22 Système pour la récupération et utilisation de gaz CO2 Expired - Lifetime EP0487102B1 (fr)

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JP318443/90 1990-11-22
JP2318443A JPH04190831A (ja) 1990-11-22 1990-11-22 炭酸ガス再資源化リサイクルシステム

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WO2003080223A1 (fr) * 2002-03-22 2003-10-02 Consejo Superior De Investigaciones Científicas Procede de combustion integrant une separation de co2 realisee par carbonatation
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US5352366A (en) * 1992-08-13 1994-10-04 Aquafrance Method for purifying liquid fuel boiler smoke by cooling and washing the smoke and neutralizing the effluents
EP0583197A1 (fr) * 1992-08-13 1994-02-16 Aquafrance Procédé de dépollution de fumées de chaudières à combustible liquide par refroidissement et lavage des fumées, et neutralisation des effluents
WO1994012266A1 (fr) * 1992-11-29 1994-06-09 Hamit Energy As Procede de reduction de la pollution atmospherique
US5958353A (en) * 1992-11-29 1999-09-28 Clue Method for reducing atmospheric pollution
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US5665319A (en) * 1994-07-12 1997-09-09 Director-General Of Agency Of Industrial Science And Technology Method of separating carbon dioxide from carbon dioxide containing gas and combustion apparatus having function to separate carbon dioxide from the combustion gas
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US6890497B2 (en) * 1998-08-18 2005-05-10 The United States Of America As Represented By The United States Department Of Energy Method for extracting and sequestering carbon dioxide
WO2000010691A1 (fr) * 1998-08-18 2000-03-02 United States Department Of Energy Procede et appareil permettant d'extraire et de sequestrer le dioxyde de carbone
US7655193B1 (en) * 1998-08-18 2010-02-02 The United States Of America As Represented By The United States Department Of Energy Apparatus for extracting and sequestering carbon dioxide
EP1129997A3 (fr) * 1999-05-17 2002-08-28 Mitsubishi Heavy Industries, Ltd. Désulfurisation de gaz de combustion
WO2001005489A1 (fr) * 1999-07-19 2001-01-25 Ebara Corporation Appareil et procede d'epuration de gaz acide
EP1193444A1 (fr) * 2000-09-27 2002-04-03 ALSTOM Power N.V. Procédé pour réduire simultanément les émissions de CO2 et de SO2 dans une installation de combustion
FR2824493A1 (fr) * 2001-05-09 2002-11-15 Yvan Alfred Schwob Recyclage du gaz carbonique par retroconversion oxydoreductrice
ES2192994A1 (es) * 2002-03-22 2003-10-16 Consejo Superior Investigacion Procedimiento de combustion con separacion integrada de co2 mediante carbonatacion.
WO2003080223A1 (fr) * 2002-03-22 2003-10-02 Consejo Superior De Investigaciones Científicas Procede de combustion integrant une separation de co2 realisee par carbonatation
GB2418430A (en) * 2004-09-10 2006-03-29 Itm Fuel Cells Ltd Sequestration of carbon dioxide
DE102008027311A1 (de) * 2008-06-07 2009-12-10 Deutz Ag Verwendung von Kohlenstoffdioxid aus Verbrennungsabgasen und solar erzeugtem Wasserstoff zur Herstellung flüssiger Brennstoffe
WO2010115871A1 (fr) * 2009-04-08 2010-10-14 Shell Internationale Research Maatschappij B.V. Procédé de traitement d'un courant de gaz d'échappement et appareil pour la mise en oeuvre de ce procédé
US20120058545A1 (en) * 2009-04-08 2012-03-08 Sandra Schreuder Method of treating an off-gas stream and an apparatus therefor
CN102413900A (zh) * 2009-04-08 2012-04-11 国际壳牌研究有限公司 处理尾气物流的方法和设备
US8765451B2 (en) 2009-04-08 2014-07-01 Shell Oil Company Method of treating an off-gas stream and an apparatus therefor
CN102389695B (zh) * 2010-07-08 2015-02-18 气体产品与化学公司 吸附剂在含氧燃料酸压缩中的使用
CN102389695A (zh) * 2010-07-08 2012-03-28 气体产品与化学公司 吸附剂在含氧燃料酸压缩中的使用
EP3549660A1 (fr) * 2011-05-10 2019-10-09 Universidad De Sevilla Procédé de capture de co2 et de so2
EP2754482A1 (fr) * 2011-05-10 2014-07-16 Universidad De Sevilla Procédé de capture de co2 et de so2
EP2754482A4 (fr) * 2011-05-10 2015-04-29 Univ Sevilla Procédé de capture de co2 et de so2
JP2013092065A (ja) * 2011-10-24 2013-05-16 Hitachi Zosen Corp 複合型火力発電システム
EP3559154A4 (fr) * 2016-12-23 2020-08-05 Carbon Engineering Ltd. Procédé et système de synthèse de carburant à partir d'une source diluée de dioxyde de carbone
IL267507B1 (en) * 2016-12-23 2023-04-01 Carbon Eng Ltd Method and system for synthesizing fuel from a dissolved carbon dioxide source
US11655421B2 (en) 2016-12-23 2023-05-23 Carbon Engineering Ltd. Method and system for synthesizing fuel from dilute carbon dioxide source
AU2017383560B2 (en) * 2016-12-23 2023-05-25 Carbon Engineering Ltd. Method and system for synthesizing fuel from dilute carbon dioxide source
IL267507B2 (en) * 2016-12-23 2023-08-01 Carbon Eng Ltd Method and system for synthesizing fuel from a dissolved carbon dioxide source
CN112337298A (zh) * 2020-10-19 2021-02-09 华中科技大学 一种富氧烟气制碳氢燃料协同脱硫的光催化反应器及方法
CN112337298B (zh) * 2020-10-19 2021-08-03 华中科技大学 一种富氧烟气制碳氢燃料协同脱硫的光催化反应器及方法

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EP0487102B1 (fr) 1995-08-02
DE69111754D1 (de) 1995-09-07
DE69111754T2 (de) 1995-11-23
JPH04190831A (ja) 1992-07-09

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